Lubricant Compositions Containing Phosphates and/or Phosphites and Methods of Making and Using Same

ABSTRACT

A lubricant compositions having at least one base oil composition and a friction-reducing composition including a substituted phosphate ester and/or substituted hydrogen phosphites are described. Methods for making such compounds and methods of drilling using such lubricant compositions are also described.

CROSS REFERENCE TO RELATED APPLICATIONS

This invention claims priority to and the benefit of U.S. Ser. No.62/186,516, filed Jun. 30, 2015, which is incorporated by referenceherein.

This invention relates to U.S. Ser. No. 62/186,503, filed Jun. 30, 2015,entitled “Glycerol Carbamate Based Lubricant Compositions and Methods ofMaking and Using Same”, (Attorney Docket 2015EM141); U.S. Ser. No.62/186,494, filed Jun. 30, 2015, entitled “Lubricant Compositions andMethods of Making and Using Same”, (Attorney Docket 2015EM142); U.S.Ser. No. 62/186,509, filed Jun. 30, 2015, entitled “LubricantCompositions and Methods of Making and Using Same”, (Attorney Docket2015EM143); and U.S. Ser. No. 62/186,526, filed Jun. 30, 2015, entitled“Lubricant Compositions Comprising Diol Functional Groups and Methods ofMaking and Using Same”, (Attorney Docket 2015EM145).

FIELD OF THE INVENTION

The present disclosure relates to lubricant compositions and drillingfluid compositions useful in drilling of wellbores.

BACKGROUND OF THE INVENTION

The process of drilling a hole in the ground for the extraction of anatural resource requires a fluid for removing the cuttings from thewellbore, lubricating and cooling the drill bit, controlling formationpressures and maintaining hole stability.

Many formations present difficulties for drilling. For example, thehorizontal displacement that occurs in extended reach drilling (ERD) isoften limited by torque and drag losses due to friction. Surfaceinteractions, such as rotation of the drill string, is believed tocontribute to such frictional losses. In extended reach, drillingfrictional losses can be reduced by using a hydrocarbon-based drillingfluid. Additives can be added to the hydrocarbon-based fluid to furtherreduce the frictional losses.

Nevertheless, extended reach drilling could be more useful if longerwellbores could be effectively drilled. Thus, there is need in the artfor new lubricant compositions, e.g., for use in drilling operations,particularly extended reach drilling.

SUMMARY OF THE INVENTION

The subject matter of this application relates, in part, to thediscovery that certain phosphate and phosphite compositions, when addedto a base oil composition that includes water, can significantly reducethe coefficient of friction experienced during drilling. It is believedthat such reductions in the coefficient of friction can lead to improveddrilling, particularly to drill longer wellbores.

Thus, in one aspect, the subject matter of this application relates tolubricant compositions suitable for use in drilling operations,comprising: a) about 90 to 99 wt % of at least one base oil composition,the base oil composition comprising about 1.0 to about 15.0 wt % water,and b) about 1.0 to about 10.0 wt % of a friction-reducing compositioncomprising: at least one compound represented by Formula I:

wherein each R¹ to R⁴ is selected from the group consisting of H andbranched or unbranched, substituted or unsubstituted C₁ to C₂₀hydrocarbyl groups;

R⁵ is selected from the group consisting of H and branched orunbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbyl groupsand polyethylene glycol groups having the formula O(CH₂CH₂O)_(n)R′,wherein R′ is H or a branched or unbranched, substituted orunsubstituted C₁ to C₂₀ hydrocarbyl group and n may be from 1 to about50;

each R⁶ and R⁷ is individually selected from the group consisting of H,branched or unbranched, substituted or unsubstituted C₁ to C₁₀₀hydrocarbyl groups, and branched or unbranched, substituted orunsubstituted C₁ to C₁₀₀ alkoxyhydrocarbyl groups;

y may be an integer from 1 to 47; and z may be an integer from 0 to 47.

In another aspect, the subject matter of this application relates tolubricant compositions suitable for use in drilling operations made by aprocess, comprising: a) providing at least one base oil composition, thebase oil composition comprising about 1.0 to about 15.0 wt % water, andb) combining about 90 to about 99.0 wt % of the base oil compositionwith about 1.0 to about 10.0 wt % of a friction-reducing compositioncomprising: a compound represented by Formula I.

In another aspect, the subject matter of this application relates tomethods of making a lubricant composition suitable for use in drillingoperations. The methods comprise a) providing at least one base oilcomposition, the base oil composition comprising about 1.0 to about 15.0wt % water, and b) combining about 90 to about 99.0 wt % of the base oilcomposition with about 1.0 to about 10.0 wt % of a friction-reducingcomposition comprising: a compound represented by Formula I.

In still another aspect, the subject matter of this application relatesto methods of drilling a wellbore. The methods comprise: a) providing afriction-reducing composition prepared by mixing i) greater than orequal to about 90 wt % of at least one base oil composition, the baseoil composition comprising about 1.0 to about 15.0 wt % water, and ii)from about 1.0 to about 10.0 wt % of a friction-reducing compositioncomprising: a compound represented by Formula I; and b) introducing thelubricant composition into the wellbore.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the terms “well” and “wellbore” are used interchangeablyand can include, without limitation, an oil, gas or water productionwell, an injection well, or a geothermal well. As used herein, a “well”includes at least one wellbore. A wellbore can include vertical,inclined, and horizontal portions, and it can be straight, curved, orbranched. As used herein, the term “wellbore” includes any cased, andany uncased, open-hole portion of the wellbore. A near-wellbore regionis the subterranean material and rock of the subterranean formationsurrounding the wellbore. As used herein, a “well” also includes thenear-wellbore region. The near-wellbore region is generally consideredto be the region within about 10 feet of the wellbore. As used herein,“into a well” means and includes into any portion of the well, includinginto the wellbore or into the near-wellbore region via the wellbore.

A portion of a wellbore may be an open hole or cased hole. In anopen-hole wellbore portion, a tubing or drill string may be placed intothe wellbore. The tubing or drill string allows fluids to be circulatedin the wellbore. In a cased-hole wellbore portion, a casing is placedand cemented into the wellbore, which can also contain a tubing or drillstring. The space between two cylindrical shapes is called an annulus.Examples of an annulus include, but are not limited to: the spacebetween the wellbore and the outside of a tubing or drill string in anopen-hole wellbore; the space between the wellbore and the outside of acasing in a cased-hole wellbore; and the space between the inside of acasing and the outside of a tubing or drill string in a cased-holewellbore.

For the purpose of this invention, friction means the mechanicalresistance and rubbing of the drill string with the cased hole and theopen hole as the drill string or tubing is moved, withdrawn, advanced orrotated. Furthermore it also comprises the mechanical resistance ofcoiled tubing inside the cased and the open hole; introducing casing;introducing screens; introducing tools for cleaning, fracturing, andperforating; rotating drill string; advancing the wellbore; withdrawinga drill string; and/or withdrawing coiled tubing.

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as described inChemical and Engineering News, (1985), Vol. 63(5), pg. 27.

The terms “hydrocarbyl radical,” “hydrocarbyl,” “hydrocarbyl group,”“alkyl radical,” and “alkyl” are used interchangeably throughout thisdocument. Likewise the terms “group,” “radical,” and “substituent” arealso used interchangeably in this document. For purposes of thisdisclosure, “hydrocarbyl radical” is defined to be C₁-C₅₀ radicals, thatmay be linear, branched, or cyclic, and when cyclic, aromatic ornon-aromatic. Examples of such radicals include, but are not limited to,methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cyclooctyl, and the like including theirsubstituted analogues. Substituted hydrocarbyl radicals are radicals inwhich at least one hydrogen atom of the hydrocarbyl radical has beensubstituted with at least one functional group such as NR*₂, OR*, SeR*,TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and thelike, or where at least one heteroatom has been inserted within ahydrocarbyl ring.

The term “alkenyl” means a straight-chain, branched-chain, or cyclichydrocarbon radical having one or more double bonds. These alkenylradicals may be optionally substituted. Examples of suitable alkenylradicals include, but are not limited to, ethenyl, propenyl, allyl,1,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl,cyclooctenyl, and the like, including their substituted analogues.

The term “alkoxy” or “alkoxide” means an alkyl ether or aryl etherradical wherein the term alkyl is as defined above. Examples of suitablealkyl ether radicals include, but are not limited to, methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,phenoxy, and the like.

The term “aryl” or “aryl group” means a six carbon aromatic ring and thesubstituted variants thereof, including but not limited to, phenyl,2-methyl-phenyl, xylyl, and 4-bromo-xylyl. Likewise heteroaryl means anaryl group where a ring carbon atom (or two or three ring carbon atoms)has been replaced with a heteroatom, preferably N, O, or S. As usedherein, the term “aromatic” also refers to pseudoaromatic heterocycleswhich are heterocyclic substituents that have similar properties andstructures (nearly planar) to aromatic heterocyclic ligands, but are notby definition aromatic; likewise, the term aromatic also refers tosubstituted aromatics.

Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist(e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl) reference to onemember of the group (e.g., n-butyl) shall expressly disclose theremaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in thefamily. Likewise, reference to an alkyl, alkenyl, alkoxide, or arylgroup without specifying a particular isomer (e.g., butyl) expresslydiscloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, andtert-butyl).

As used herein, the term “heterogeneous blend” means a compositionhaving two or more morphological phases in the same state. For example ablend of immiscible components, e.g., oil and water, where one componentforms discrete packets dispersed in a matrix of another component issaid to be heterogeneous. By continuous phase is meant the matrix phasein a heterogeneous blend. By discontinuous phase is meant the dispersedphase in a heterogeneous blend.

Kinematic viscosity (also referred to as viscosity) is determined byASTM D 445, and is typically measured at 40° C. (Kv40) or 100° C.(Kv100). If temperature is not indicated, the viscosity is Kv100.

Lubricant Composition

Lubricant compositions that are the subject of this disclosure typicallycomprise a base oil composition and a friction-reducing agent. The baseoil composition is typically present in the lubricant composition in anamount of ≧ about 50.0 wt %, ≧ about 55.0 wt %, ≧ about 60.0 wt %, ≧about 65.0 wt %, ≧ about 70.0 wt %, ≧ about 75.0 wt %, ≧ about 80.0 wt%, ≧ about 85.0 wt %, ≧ about 90.0 wt %, ≧ about 95.0 wt %, or ≧ about97.0 wt %, of the lubricant composition. Additionally or alternatively,the lubricant composition comprises ≦ about 99.0 wt %, e.g., ≦ about97.0 wt %, ≦ about 95.0 wt %, ≦ about 90.0 wt %, ≦ about 80.0 wt %, ≦about 75.0 wt %, ≦ about 70.0 wt %, ≦ about 65.0 wt %, ≦ about 60.0 wt%, ≦ or about 55.0 wt %, base oil composition. Ranges of the amount ofbase oil composition in the lubricant composition include ranges formedfrom any combination of the above-enumerated values, e.g., about 50.0 toabout 99.0 wt %, about 55.0 to about 97.0 wt %, about 60.0 to about 95.0wt %, about 65.0 to about 90.0 wt %, about 70.0 to about 85.0 wt %,about 75.0 to about 80.0 wt %, about 70.0 to about 95.0 wt %, about 85.0to about 95.0 wt %, etc.

In a preferred embodiment of the invention, the base oil compositioncomprises a base oil that is present in the lubricant composition inranges from about 50.0 to about 99.0 wt %, about 55.0 to about 97.0 wt%, about 60.0 to about 95.0 wt %, about 65.0 to about 90.0 wt %, about70.0 to about 85.0 wt %, about 75.0 to about 80.0 wt %, about 70.0 toabout 95.0 wt %, about 85.0 to about 95.0 wt %, and thefriction-reducing composition is typically present in the lubricantcomposition in the amount of about 0.5 to about 10.0 wt %, about 1.0 toabout 9.0 wt %, about 1.5 to about 8.0 wt %, about 2.0 to about 7.0 wt%, about 2.5 to about 6.0 wt %, about 3.0 to about 5.0 wt %, about 3.5to about 4.5 wt %, about 1.0 to about 5.0 wt %, about 2.0 to about 4.0wt %.

The friction-reducing composition is typically present in the lubricantcomposition in an amount of ≧ about 0.5 wt %, e.g., ≧ about 1.0 wt %, ≧about 1.5 wt %, ≧ about 2.0 wt %, ≧ about 2.5 wt %, ≧ about 3.0 wt %, ≧about 3.5 wt %, ≧ about 4.0 wt %, ≧ about 4.5 wt %, ≧ about 5.0 wt %, ≧about 6.0 wt %, ≧ about 7.0 wt %, ≧ about 8.0 wt %, or ≧ about 9.0 wt %.Additionally or alternatively, the lubricant composition comprises ≦about 10.0 wt % e.g., ≦ about 9.0 wt %, ≦ about 8.0 wt %, ≦ about 7.0 wt%, ≦ about 6.0 wt %, ≦ about 5.0 wt %, ≦ about 4.5 wt %, ≦ about 4.0 wt%, ≦ about 3.5 wt %, ≦ about 3.0 wt %, ≦ about 2.5 wt %, ≦ about 2.0 wt%, ≦ about 1.5 wt %, or ≦ about 1.0 wt %, friction-reducing agent.Ranges of the amount of friction-reducing composition in the lubricantcomposition include ranges formed from any combination of theabove-enumerated values, e.g., about 0.5 to about 10.0 wt %, about 1.0to about 9.0 wt %, about 1.5 to about 8.0 wt %, about 2.0 to about 7.0wt %, about 2.5 to about 6.0 wt %, about 3.0 to about 5.0 wt %, about3.5 to about 4.5 wt %, about 1.0 to about 5.0 wt %, about 2.0 to about4.0 wt %, about 0.1 wt % to about 6.0 wt %, etc.

All weight percentages are based on the total weight of the base oil andthe friction-reducing compositions.

Lubricant compositions generally have a coefficient of friction lessthan that of the base oil composition. Some lubricant compositions havea coefficient of friction of ≦ about 0.12, e.g., ≦ about 0.10, ≦ about0.08, ≦ about 0.06, ≦ about 0.04, or ≦ about 0.02. Additionally oralternatively, the coefficient of friction may be ≧ about 0.01, e.g., ≧about 0.03, ≧ about 0.05, ≧ about 0.07, ≧ about 0.09, or ≧ about 0.11.Ranges of the coefficient of friction of the lubricant compositioninclude ranges formed from any combination of the above-enumeratedvalues, e.g., about 0.01 to about 0.12, about 0.3 to about 0.10, about0.05 to about 0.08, about 0.06 to about 0.07, about 0.08 to about 0.12,about 0.08 to about 0.10, etc.

Additionally or alternatively, the lubricant composition may becharacterized by a change in the coefficient of friction relative to thecoefficient of friction of the base oil composition without thefriction-reducing agent. In other words, the lubricant compositionhaving the friction reducing agent may have a coefficient of frictionthat is at least about 20.0% lower than, (alternately, is at least about25.0% lower than, is at least about 30.0% lower than, is at least about35.0% lower than, is at least about 40.0% lower than, is at least about45.0% lower than, is at least about 50.0% lower than, is at least about55.0% lower than, is at least about 60.0% lower than), the coefficientof friction of the base oil composition in the absence of the additivecomposition. Ranges of the reduction in the coefficient of friction ofthe lubricant composition relative to the base oil composition withoutthe friction-reducing composition include ranges formed from anycombination of the above-enumerated values, e.g., about 20.0 to about60.0% lower, about 25.0 to about 55.0% lower, about 30.0 to about 50.0%lower, about 35.0 to about 45.0% lower, about 40.0% lower, about 30.0 toabout 60.0% lower, about 35.0 to about 60.0% lower, about 40.0 to about60.0% lower, about 45.0 to about 60.0% lower, about 40.0 to about 55.0%lower, etc. For clarity, an exemplary lubricant composition may comprise4.0 g of friction reducing agent and 96.0 g of a base oil compositioncomprising 86.0 g of base oil and 10.0 g of other additives. Thereduction in the coefficient of friction would be determined bycomparing the coefficient of friction of this exemplary compositionwould be compared to the coefficient of friction of a compositioncomprising 86.0 g base oil and 10.0 g of the other additives.

Base Oil Composition

Generally, the base oil composition may include a base oil and one ormore base oil additives. Numerous base oils are known in the art.Particular base oils that are useful in the present disclosure includeboth natural oils and synthetic oils, as well as unconventional oils (ormixtures thereof), which can be used unrefined, refined, or re-refined(the latter is also known as reclaimed or reprocessed oil). Unrefinedoils are those obtained directly from a natural or synthetic source andused without added purification. These include shale oil obtaineddirectly from retorting operations, petroleum oil obtained directly fromprimary distillation, and ester oil obtained directly from anesterification process. Refined oils are similar to the oils discussedfor unrefined oils except refined oils are subjected to one or morepurification steps to improve at least one base oil property. Oneskilled in the art is familiar with many purification processes. Theseprocesses include solvent extraction, secondary distillation, acidextraction, base extraction, filtration, and percolation. Re-refinedoils are obtained by processes analogous to refined oils but using anoil that has been previously used as a feed stock.

Groups I, II, III, IV, and V are broad lube base oil stock categoriesdeveloped and defined by the American Petroleum Institute (APIPublication 1509; www.API.org) to create guidelines for base oils. GroupI base stocks have a viscosity index of 80 to 120 and contain >0.03%sulfur and/or less than 90% saturates. Group II base stocks have aviscosity index of 80 to 120, and contain ≦0.03% sulfur and ≧90%saturates. Group III stocks have a viscosity index ≧120 and contain≦0.03% sulfur and ≧90% saturates. Group IV includes polyalphaolefins(PAO) and Gas-to-Liquid (GTL) materials. Group V base stock includesbase stocks not included in Groups I-IV. The table below summarizesproperties of each of these five groups.

Exemplary Base Oil Properties Saturates (wt %) Sulfur (wt %) ViscosityIndex (cSt) Group I <90 and/or >0.03 and/or 80 to 120 Group II ≧90 and≦0.03 and 80 to 120 Group III ≧90 and ≦0.03 and ≧120 Group IV IncludesPAO's and GTL's Group V All other base oil stocks not included in GroupsI-IV

Useful GTL's include those described as high purity hydrocarbonfeedstocks at paragraphs [0245]-[0303] of US 2008/0045638. PAO's usefulherein include those described in paragraphs [0243]-[0266] of US2008/0045638. Useful Group III Base Oils include those described atparagraphs [0304]-[0306] of US 2008/0045638.

Natural oils include animal oils, vegetable oils (castor oil and lardoil, for example), and mineral oils. Animal and vegetable oilspossessing favorable thermal oxidative stability can be used. Of thenatural oils, mineral oils are preferred. Mineral oils vary widely as totheir crude source, for example, as to whether they are paraffinic,naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal orshale are also useful. Natural oils vary also as to the method used fortheir production and purification, for example, their distillation rangeand whether they are straight run or cracked, hydrorefined, or solventextracted.

Group II and/or Group III hydroprocessed or hydrocracked basestocks,including synthetic oils, are also well known basestock oils.

Synthetic oils include hydrocarbon oil. Hydrocarbon oils include oilssuch as polymerized and interpolymerized olefins (polybutylenes,polypropylenes, propylene isobutylene copolymers, ethylene-olefincopolymers, and ethylene-alphaolefin copolymers, for example).Polyalphaolefin (PAO) oil base stocks are commonly used synthetichydrocarbon oil. By way of example, PAOs derived from C₈ to C₁₄ olefins,e.g., C₈, C₁₀, C₁₂, C₁₄ olefins or mixtures thereof may be utilized.Some such PAO's are described in U.S. Pat. No. 4,956,122; U.S. Pat. No.4,827,064; and U.S. Pat. No. 4,827,073, each of which is incorporatedherein by reference in its entirety.

The number average molecular weights of the PAOs, which are knownmaterials and generally available on a major commercial scale fromsuppliers such as ExxonMobil Chemical Company, Chevron Phillips ChemicalCompany, BP, and others, typically vary from 250 to 3,000 g/mol,although PAO's may be made in Kinematic viscosities up to 3500 cSt (100°C.). The PAOs are typically comprised of relatively low molecular weighthydrogenated polymers or oligomers of alphaolefins which include, butare not limited to, C₂ to C₃₂ alphaolefins with the C₈ to C₁₆alphaolefins, such as 1-octene, 1-decene, 1-dodecene and the like, beingpreferred. The preferred polyalphaolefins are poly-1-octene,poly-1-decene and poly-1-dodecene and mixtures thereof and mixedolefin-derived polyolefins. However, the dimers of higher olefins in therange of C₁₄ to C₁₈ may be used to provide low viscosity basestocks ofacceptably low volatility. Depending on the viscosity grade and thestarting oligomer, the PAOs may be predominantly trimers and/ortetramers of the starting olefins, with minor amounts of the higheroligomers, having a viscosity range of 1.5 to 3500 cSt (Kv100), such asfrom 1.5 to 12 cSt.

The PAO fluids may be conveniently made by the polymerization of analphaolefin in the presence of a polymerization catalyst such as theFriedel-Crafts catalysts including, for example, aluminum trichloride,boron trifluoride or complexes of boron trifluoride with water, alcoholssuch as ethanol, propanol or butanol, carboxylic acids or esters such asethyl acetate or ethyl propionate. For example the methods disclosed byU.S. Pat. No. 4,149,178 or U.S. Pat. No. 3,382,291 may be convenientlyused herein. Other descriptions of PAO synthesis are found in thefollowing U.S. Pat. No. 3,742,082; U.S. Pat. No. 3,769,363; U.S. Pat.No. 3,876,720; U.S. Pat. No. 4,239,930; U.S. Pat. No. 4,367,352; U.S.Pat. No. 4,413,156; U.S. Pat. No. 4,434,408; U.S. Pat. No. 4,910,355;U.S. Pat. No. 4,956,122; and U.S. Pat. No. 5,068,487. The dimers of theC₁₄ to C₁₈ olefins are described in U.S. Pat. No. 4,218,330. The PAO'smay be produced using a metallocene catalyst compound as described inU.S. Pat. No. 8,535,514 and U.S. Pat. No. 8,247,358.

The hydrocarbyl aromatics can be used as base oil or base oil componentand can be any hydrocarbyl molecule that contains at least 5% of itsweight derived from an aromatic moiety such as a benzenoid moiety ornaphthenoid moiety, or their derivatives. These hydrocarbyl aromaticsinclude alkyl benzenes, alkyl naphthalenes, alkyl diphenyl oxides, alkylnaphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylatedthiodiphenol, and the like. The aromatic can be mono-alkylated,dialkylated, polyalkylated, and the like. The aromatic can be mono- orpoly-functionalized. The hydrocarbyl groups can also be comprised ofmixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl groups,cycloalkenyl groups and other related hydrocarbyl groups. Thehydrocarbyl groups can range from C₆ to C₆₀ with a range of C₈ to C₂₀often being preferred. A mixture of hydrocarbyl groups is oftenpreferred, and up to three such substituents may be present. Thehydrocarbyl group can optionally contain sulfur, oxygen, and/or nitrogencontaining substituents. The aromatic group can also be derived fromnatural (petroleum) sources, provided at least 5% of the molecule iscomprised of an above-type aromatic moiety. Viscosities at 100° C. ofapproximately 3 cSt to 50 cSt are preferred, with viscosities ofapproximately 3.4 cSt to 20 cSt often being more preferred for thehydrocarbyl aromatic component. In one embodiment, an alkyl naphthalenewhere the alkyl group is primarily comprised of 1-hexadecene is used.Other alkylates of aromatics can be advantageously used. Naphthalene ormethyl naphthalene, for example, can be alkylated with olefins such asoctene, decene, dodecene, tetradecene or higher, mixtures of similarolefins, and the like. Useful concentrations of hydrocarbyl aromatic ina base oil composition can be 2% to 25%, preferably 4% to 20%, and morepreferably 4% to 15%, depending on the application.

Other useful fluids for use as base oils include non-conventional orunconventional base stocks that have been processed, preferablycatalytically, or synthesized to provide high performancecharacteristics.

Non-conventional or unconventional base stocks/base oils include one ormore of a mixture of base stock(s) derived from one or moreGas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate basestock(s) derived from natural wax or waxy feeds, mineral and ornon-mineral oil waxy feed stocks such as slack waxes, natural waxes, andwaxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxyraffinate, hydrocrackate, thermal crackates, or other mineral, mineraloil, or even non-petroleum oil derived waxy materials such as waxymaterials received from coal liquefaction or shale oil, and mixtures ofsuch base stocks.

GTL materials are materials that are derived via one or more synthesis,combination, transformation, rearrangement, and/ordegradation/deconstructive processes from gaseous carbon-containingcompounds, hydrogen-containing compounds and/or elements as feed stockssuch as hydrogen, carbon dioxide, carbon monoxide, water, methane,ethane, ethylene, acetylene, propane, propylene, propyne, butane,butylenes, and butynes. GTL base stocks and/or base oils are GTLmaterials of base oil viscosity that are generally derived fromhydrocarbons; for example, waxy synthesized hydrocarbons, that arethemselves derived from simpler gaseous carbon-containing compounds,hydrogen-containing compounds and/or elements as feed stocks. GTL basestock(s) and/or base oil(s) include oils boiling in the lube oil boilingrange (1) separated/fractionated from synthesized GTL materials such as,for example, by distillation and subsequently subjected to a final waxprocessing step which involves either or both of a catalytic dewaxingprocess, or a solvent dewaxing process, to produce lube oils ofreduced/low pour point; (2) synthesized wax isomerates, comprising, forexample, hydrodewaxed or hydroisomerized catalytic and/or solventdewaxed synthesized wax or waxy hydrocarbons; (3) hydrodewaxed orhydroisomerized catalytic and/or solvent dewaxed Fischer-Tropsch (F-T)material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possibleanalogous oxygenates); preferably hydrodewaxed orhydroisomerized/followed by catalytic and/or solvent dewaxing dewaxedF-T waxy hydrocarbons, or hydrodewaxed or hydroisomerized/followed bycatalytic (or solvent) dewaxing dewaxed, F-T waxes, or mixtures thereof.

GTL base stock(s) and/or base oil(s) derived from GTL materials,especially, hydrodewaxed or hydroisomerized/followed by catalytic and/orsolvent dewaxed wax or waxy feed, preferably F-T material derived basestock(s) and/or base oil(s), are characterized typically as havingKinematic viscosities at 100° C. of from 2 cSt to 50 cSt (ASTM D445).They are further characterized typically as having pour points of −5° C.to −40° C. or lower (ASTM D97). They are also characterized typically ashaving viscosity indices of 80 to 140 or greater (ASTM D2270).

In addition, the GTL base stock(s) and/or base oil(s) are typicallyhighly paraffinic (>90% saturates), and may contain mixtures ofmonocycloparaffins and multicycloparaffins in combination withnon-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stock(s) and/or base oil(s)typically have very low sulfur and nitrogen content, generallycontaining less than 10 ppm, and more typically less than 5 ppm of eachof these elements. The sulfur and nitrogen content of GTL base stock(s)and/or base oil(s) obtained from F-T material, especially F-T wax, isessentially nil. In addition, the absence of phosphorous and aromaticsmake this materially especially suitable for the formulation of low SAPproducts.

The term GTL base stock and/or base oil and/or wax isomerate base stockand/or base oil is to be understood as embracing individual fractions ofsuch materials of wide viscosity range as recovered in the productionprocess, mixtures of two or more of such fractions, as well as mixturesof one or two or more low viscosity fractions with one, two or morehigher viscosity fractions to produce a blend wherein the blend exhibitsa target Kinematic viscosity.

The GTL material, from which the GTL base stock(s) and/or base oil(s)is/are derived is preferably an F-T material (i.e., hydrocarbons, waxyhydrocarbons, wax). In addition, the GTL base stock(s) and/or baseoil(s) are typically highly paraffinic (>90% saturates), and may containmixtures of monocycloparaffins and multicycloparaffins in combinationwith non-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stock(s) and/or base oil(s) andhydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed basestock(s) and/or base oil(s) typically have very low sulfur and nitrogencontent, generally containing less than 10 ppm, and more typically lessthan 5 ppm of each of these elements. The sulfur and nitrogen content ofGTL base stock(s) and/or base oil(s) obtained from F-T material,especially F-T wax, is essentially nil. In addition, the absence ofphosphorous and aromatics make this material especially suitable for theformulation of low sulfur, sulfated ash, and phosphorus (low SAP)products.

Base oils for use in the formulated base oil compositions useful in thepresent disclosure are any of the variety of oils corresponding to APIGroup I, Group II, Group III, Group IV, and Group V oils and mixturesthereof, preferably API Group II, Group III, Group IV, and Group V oilsand mixtures thereof, more preferably the Group III to Group V base oilsdue to their exceptional volatility, stability, viscometric andcleanliness features. Minor quantities of Group I stock, such as theamount used to dilute additives for blending into formulated lube oilproducts, can be tolerated but should be kept to a minimum, i.e.,amounts only associated with their use as diluents/carrier oil foradditives used on an “as-received” basis. Even in regard to the Group IIstocks, it is preferred that the Group II stock be in the higher qualityrange associated with that stock, i.e., a Group II stock having aviscosity index in the range of 100 to 120.

Some base oils may have an ester content ≦ about 50 wt %, e.g., ≦ about40 wt %, ≦ about 30 wt %, ≦ about 5.0 wt %, or ≦ about 1.0 wt %.Additionally or alternatively, some base oils may have an ester content≧ about 40 wt %, e.g., ≧ about 50 wt %, ≧ about 70 wt %, or ≧ about 90wt %.

Some base oils may have an aromatic contents ≦ about 15.0 wt %, e.g., ≦about 10.0 wt %, ≦ about 5.0 wt %, ≦ about 1.0 wt %, ≦ about 0.50 wt %,≦ about 0.10 wt %, ≦ about 0.05 wt %, ≦ about 0.01 wt %, or ≦ about0.005 wt %. Additionally or alternatively, the aromatics content may be≧ about 0.005 wt %, e.g., ≧ about 0.01 wt %, ≧ about 0.05 wt %, ≧ about0.10 wt %, ≧ about 0.5 wt %, ≧ about 0.1 wt %, ≧ about 1.0 wt %, ≧ about5.0 wt %, or ≧ about 10.0 wt %. Ranges of the aromatics contentexpressly disclosed herein include all combinations of theabove-enumerated values, e.g., about 0.005 to about 15.0 wt %, about0.01 to about 10.0 wt %, about 0.05 to about 5.0 wt %, about 0.10 toabout 1.0 wt %, etc.

Some exemplary base oils have been characterized by their Kinematicviscosity at 40° C. (Kv40). For example, particular base oils may have aviscosity ≧ about 1.0 cSt, e.g., ≧ about 1.3 cSt, ≧ about 1.5 cSt, ≧about 1.7 cSt, ≧ about 1.9 cSt, ≧ about 2.1 cSt, ≧ about 2.3 cSt, ≧about 2.5 cSt, ≧ about 2.7 cSt, ≧ about 2.9 cSt, ≧ about 3.1 cSt, ≧about 3.3 cSt, ≧ about 3.5 cSt, ≧ about 3.7 cSt, ≧ about 4.0 cSt, ≧about 4.5 cSt, or ≧ about 4.8 cSt, at 40° C. Additionally oralternatively, the viscosity at 40° C. may be ≦ about 5.0 cSt, e.g., ≦about 4.8 cSt, ≦ about 4.5 cSt, ≦ about 4.0 cSt, ≦ about 3.7 cSt, ≦about 3.5 cSt, ≦ about 3.3 cSt, ≦ about 3.1 cSt, ≦ about 2.9 cSt, ≦about 2.7 cSt, ≦ about 2.5 cSt, ≦ about 2.3 cSt, ≦ about 2.1 cSt, ≦about 1.9 cSt, ≦ about 1.7 cSt, ≦ about 1.5 cSt, ≦ about 1.3 cSt, or ≦about 1.1 cSt, at 40° C. Some such base oils are available fromExxonMobil Chemical Company under the tradename Escaid™, e.g., Escaid™110 comprises a desulfurized hydrogenated hydrocarbon containing lessthan 0.50 wt % aromatics and having a viscosity of about 1.7 cSt at 40°C., Escaid™ 115 having a viscosity of about 2.1 cSt at 40° C., Escaid™120 having a flash point above 100° C., and Escaid™ 120 ULA having anaromatics content <0.01 wt %.

Base Oil Additives

Often, the base oil composition includes additional additives.Preferably, one or more of the additional additives form a heterogeneousblend with the base oil. In such aspects, the base oil composition ispreferably a heterogeneous blend having base oil as the continuous phaseand one or more additional additives as the dispersed or internal phase.Alternatively or additionally, one or more of the additional additivescan solubilize in the base oil.

For example, the base oil composition can include additional additivesincluding, but not limited to, an internal phase, which is typicallywater or a brine (i.e., the base oil composition is an invertedemulsion), a pH buffer, a viscosifier, an emulsifier, a wetting agent, aweighting agent, a fluid loss additive, and a friction reducer.

For example, the base oil composition may include a pH buffer selectedfrom the group consisting of magnesium oxide, potassium hydroxide,calcium oxide, and calcium hydroxide. Commercially available examples ofa pH buffer include lime. The pH buffer can be in a concentration in therange of about 0.5 to about 10.0 pounds per barrel (ppb) of the base oilcomposition. Useful base oil compositions can have a pH ranging from alow of about 7, 8, 9, 10, 11, or 12 to a high of about 14, such as from10 to 14.

The base oil composition may optionally include a viscosifier. Theviscosifier may be selected from the group consisting of inorganicviscosifier, fatty acids, including but not limited to dimer and trimerpoly carboxylic fatty acids, diamines, polyamindes, organophilic claysand combinations thereof. Commercially available examples of a suitableviscosifier include, but are not limited to, VG-PLUS™, available fromM-I Swaco, a Schlumberger Company; RHEMOD L™, TAU-MOD™, RM-63™, andcombinations thereof, marketed by Halliburton Energy Services, Inc.According to an embodiment, the viscosifier is in a concentration of atleast 0.5 ppb of the base oil composition. The viscosifier can also bein a concentration in the range of about 0.5 to about 20 ppb,alternatively of about 0.5 to about 10 ppb, of the base oil.

The base oil composition may further include a lubricant in addition tothe friction-reducing composition described herein. In particularembodiments, the additional base oil composition comprises aparticulated material, e.g., graphite such as Steelseal™, available fromHalliburton.

The base oil composition can further include an emulsifier. Theemulsifier can be selected from the group consisting of tall oil-basedfatty acid derivatives such as amides, amines, amidoamines andimidazolines made by reactions of fatty acids and various ethanolaminecompounds, vegetable oil-based derivatives, and combinations thereofCommercially available examples of a suitable emulsifier include, butare not limited to, EZ MUL™ NT, INVERMUL™ NT, LE SUPERMUL™, andcombinations thereof, marketed by Halliburton Energy Services, Inc.,MEGAMUL™, VersaMul™, VersaCoat™, marketed by MISwaco, a SchlumbergerCompany. According to an embodiment, the emulsifier is in at least asufficient concentration such that the base oil composition maintains astable emulsion or invert emulsion. According to yet another embodiment,the emulsifier is in a concentration of at least 1 ppb of the base oilcomposition. The emulsifier can also be in a concentration in the rangeof about 1 to about 20 ppb of the base oil composition.

The base oil composition can further include a weighting agent. Theweighting agent can be selected from the group consisting of barite,hematite, manganese tetroxide, calcium carbonate, and combinationsthereof. Commercially available examples of a suitable weighting agentinclude, but are not limited to, BAROID™, BARACARB™, BARODENSE™, andcombinations thereof, marketed by Halliburton Energy Services, Inc. andMICROMAX™, marketed by Elkem. According to an embodiment, the weightingagent is in a concentration of at least 10 ppb of the base oilcomposition. The weighting agent can also be in a concentration in therange of about 10 to about 1000 ppb, such as 10 to 800 ppb, of the baseoil composition.

The base oil composition can further include a fluid loss additive. Thefluid loss additive can be selected from the group consisting ofoleophilic polymers, including crosslinked oleophilic polymers,particulates. Commercially available examples of a suitable fluid lossadditive include, but are not limited to VERSATROL™, available from M-ISwaco; N-DRIL™ HT PLUS, ADAPTA™, marketed by Halliburton EnergyServices, Inc. The fluid loss additive can also be in a concentration inthe range of about 0.5 to about 10 ppb of the base oil composition.

The base oil composition can further include an ester additive. Theester additive can be in a concentration in the range of about 1% to20%.

The base oil composition may also optionally include one or more metalsalts, MX_(y), where M is a Group 1 or Group 2 metal, X is a halogen,and y is 1 to 2. Exemplary such salts include, NaCl, KCl, CaCl₂, MgCl₂,etc. The total amount of such salts in the base oil composition istypically about 10-35 wt % in the water phase. Organic additives thatlower the water activity may also be used.

Water may also be present in the base oil composition at any convenientconcentration, typically at a relatively low concentration, e.g., ≦about 15.0 wt %, ≦ about 12.5 wt %, ≦ about 10.0 wt %, ≦ about 7.5 wt %,≦ about 5.0 wt %, ≦ about 2.5 wt %, or ≦ about 1.0 wt %, the weight %being based on the total weight of the base oil and the water.Additionally or alternatively, the concentration of water may be ≧ about0.5 wt %, e.g., ≧ about 1.0 wt %, ≧ about 2.5 wt %, ≧ about 5.0 wt %, ≧about 7.5 wt %, ≧ about 10.0 wt %, ≧ about 12.5 wt %, or ≧ about 15.0 wt%. In particular embodiments, the amount of water may be about 1 toabout 21 gallons per barrel of base oil composition, such as about 1 toabout 10 gallons per barrel of base oil composition. Range of the watercontent that are expressly disclosed comprise ranges formed from any ofthe above-enumerated values, e.g., about 0.5 to about 20.0 wt %, about0.5 to about 15.0 wt %, about 0.5 to about 12.5 wt %, about 0.5 to about10.0 wt %, about 0.5 to about 7.5 wt %, about 0.5 to about 5.0 wt %,about 0.5 to about 2.5 wt %, about 0.5 to about 1.0 wt %, about 1.0 toabout 10.0 wt %, about 1.0 to about 7.5 wt %, about 1.0 to about 5.0 wt%, about 1.0 to about 2.5 wt %, about 2.5 to about 10.0 wt %, about 2.5to about 7.5 wt %, about 2.5 to about 5.0 wt %, about 5.0 to about 10.0wt %, about 5.0 to about 7.5 wt %, etc.

The base oil can further include wetting agents. The wetting agents canbe selected from the group consisting of tall oil-based fatty acidderivatives such as amides, amines, amidoamines and imidazolines made byreactions of fatty acids and various ethanolamine compounds, vegetableoil-based derivatives, and combinations thereof. Commercially availableexamples of suitable wetting agents include, but are not limited to,DrillTreat™, OMC™, marketed by Halliburton Energy Services, Inc.,VersaWet™, marketed by MISwaco, a Schlumberger Company. According to anembodiment, the wetting agent is in at least a sufficient concentrationsuch that the base oil composition maintains a stable emulsion or invertemulsion. According to yet another embodiment, the wetting agent is in aconcentration of at least 0.25 ppb of base oil composition. The wettingagent can also be in a concentration in the range of about 0.05 to about20 ppb, such as about 0.25 to about 20 ppb of the base oil composition.

In another embodiment, the wetting agent is not present in the base oilcomposition.

Friction-Reducing Composition

Lubricant compositions according to the subject matter of the disclosurealso include at least one friction-reducing composition comprising acompound represented by Formula I:

In Formula I, each of R¹, R², R³ and R⁴ is selected from the groupconsisting of H and branched or unbranched, substituted or unsubstitutedC₁ to C₂₀ hydrocarbyl groups. Exemplary C₁ to C₂₀ hydrocarbyl groupsinclude, but are not limited to, C₂ to C₁₈, and C₄ to C₁₆, C₆ to C₁₄, C₈to C₁₂, and C₁₀ groups. The R¹, R², R³ and R⁴ hydrocarbyl groups are notlimited to unbranched hydrocarbyl groups, e.g., C₈ hydrocarbyl groupsinclude, but are not limited to, e.g., 2-ethylhexyl and 2-propylpentylgroups. Exemplary unsubstituted, unbranched hydrocarbyl groups includemethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, and octadecyl hydrocarbyl groups.

In Formula I, R⁵ is selected from the group consisting of H and branchedor unbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbylgroups. R⁵ groups are not limited to unbranched hydrocarbyl groups,e.g., C₈ hydrocarbyl groups include, but are not limited to, e.g.,2-ethylhexyl and 2-propylpentyl groups. Exemplary unsubstituted,unbranched R⁵ hydrocarbyl groups include methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl hydrocarbylgroups.

In other embodiments, R⁵ may provide a polyethylene glycol functionalityto the compound. Thus, in some embodiments, R⁵ comprises a polyethyleneglycol group having the formula —O(CH₂CH₂O)_(n)R′, wherein R′ may be Hor a branched or unbranched, substituted or unsubstituted C₁ to C₂₀hydrocarbyl groups hydrocarbyl group, e.g., C₁ to C₂₀ hydrocarbyl groupsinclude, but are not limited to, C₂ to C₁₈, and C₄ to C₁₆, C₆ to C₁₄, C₈to C₁₂, and C₁₀ groups. The R¹ hydrocarbyl group is not limited tounbranched hydrocarbyl groups, e.g., C₈ hydrocarbyl groups include, butare not limited to, e.g., 2-ethylhexyl and 2-propylpentyl groups.Exemplary unsubstituted, unbranched hydrocarbyl groups include methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, etc., hydrocarbyl groups. In such embodiments,the number of polyethylene glycol units, n, is ≧1, e.g., ≧2, ≧5, ≧7,≧10, ≧12, ≧15, ≧17, ≧20, ≧22, ≧25, ≧27, ≧30, ≧35, ≧40, or ≧45.Additionally or alternatively, n may be ≦50, e.g., ≦45, ≦40, ≦35, ≦30,≦27, ≦25, ≦22, ≦20, ≦17, ≦15, ≦12, ≦10, ≦5, or ≦2. Ranges of the numberof polyethylene glycol units, n, expressly disclosed herein compriseranges formed by any of the above-enumerated values, e.g., 1 to 50, 1 to45, 1 to 40, 1 to 35, 1 to 30, 1 to 27, 1 to 25, 1 to 22, 1 to 20, 1 to17, 1 to 15, 1 to 12, 1 to 10, 1 to 7, 1 to 5, 1 to 2, 2 to 50, 2 to 45,2 to 40, 2 to 35, 2 to 30, 2 to 27, 2 to 25, 2 to 22, 2 to 20, 2 to 17,2 to 15, 2 to 12, 2 to 10, 2 to 7, 2 to 5, etc., particularly 1 to 50, 2to 45, 5 to 40, 7 to 35, 10 to 30, 12 to 27, 15 to 25, 17 to 22, about20. Such compounds are referred to herein as “PEG-terminated” compounds.

The variable y in Formula I is ≧1, e.g., ≅2, ≧5, ≧7, ≧8, ≧10, ≧12, ≧14,≧16, ≧18, ≧20, ≧22, ≧24, ≧26, ≧28, ≧30, ≧32, ≧34, ≧36, ≧38, ≧40, ≧42, or≧44. Additionally or alternatively, y may be ≦47, e.g., ≦44, ≦42, ≦40,≦38, ≦36, ≦34, ≦32, ≦30, ≦28, ≦26, ≦24, ≦22, ≦20, ≦18, ≦16, ≦14, ≦12,≦10, ≦8, ≦7, or ≦5. In Formula I, z is ≧0, e.g., ≧1, ≧5, ≧7, ≧8,≧10,≧12, ≧14, ≧16, ≧18, ≧20, ≧22, ≧24, ≧26, ≧28, ≧30, ≧32, ≧34, ≧36,≧38, ≧40, ≧42, or ≧44. Additionally or alternatively, z may be ≦47,e.g., ≦44, ≦42, ≦40, ≦38, ≦36, ≦34, ≦32, ≦30, ≦28, ≦26, ≦24, ≦22, ≦20,≦18, ≦16, ≦14, ≦12, ≦10, ≦8, ≦7, or ≦5. Ranges of y and z values thatare expressly disclosed herein include ranges formed by any combinationof the above-recited individual values. In particular embodiments, yranges from about 5 to about 10, e.g., 8, and z ranges from about 5 toabout 10, e.g., 7, i.e., CH₃(CH₂)₇C═C(CH₂)₈—, also referred to as anoleyl group. The double bond may have cis- or trans-configuration. Inparticular embodiments, the cis-configuration may be particularlyuseful.

In Formula I, each R⁶ and R⁷ is individually selected from the groupconsisting of H, branched or unbranched, substituted or unsubstituted C₁to C₁₀₀ hydrocarbyl groups, e.g., C₁ to C₇₅ hydrocarbyl groups, C₁ toC₅₀ hydrocarbyl groups C₁ to C₂₅ hydrocarbyl groups, C₁ to C₂₀hydrocarbyl groups, C₁ to C₁₈ hydrocarbyl groups, C₁ to C₁₅ hydrocarbylgroups. Exemplary unsubstituted, unbranched hydrocarbyl groups includemethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, and octadecyl hydrocarbyl groups.

In some embodiments R⁶ and/or R⁷ are each individually selected fromhydroxy and branched or unbranched, substituted or unsubstituted C₁ toC₁₀₀ alkoxyhydrocarbyl groups, e.g., C₁ to C₇₅ alkoxyhydrocarbyl groups,C₁ to C₅₀ alkoxyhydrocarbyl groups, C₁ to C₂₅ alkoxyhydrocarbyl groups,C₁ to C₂₀ alkoxyhydrocarbyl groups, C₁ to C₁₈ alkoxyhydrocarbyl groups,C₁ to C₁₅ alkoxyhydrocarbyl groups. Exemplary unsubstituted, unbranchedalkoxyhydrocarbyl groups include methoxy, ethoxy, propoxy, butoxy,pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy,tridecoxy, tetradecoxy, pentadecoxy, hexadecoxy, heptadecoxy, andoctadecoxy alkoxyhydrocarbyl groups.

In some embodiments, R⁶ or R⁷ are independently selected from alkenylgroups. Exemplary alkenyl groups follow Formula II:

R¹²(CR¹¹ ₂)_(d)CR¹⁰═CR⁹(CR⁸ ₂)_(c)O   Formula II

In Formula II, each R⁸, R⁹, R¹⁰, and R¹¹ group in Formula II may beindividually selected from H and branched or unbranched, substituted orunsubstituted, C₁ to C₂₀ hydrocarbyl groups. Exemplary C₁ to C₂₀hydrocarbyl groups include, but are not limited to, C₂ to C₁₈, and C₄ toC₁₆, C₆ to C₁₄, C₈ to C₁₂, and C₁₀ groups. The hydrocarbyl groups arenot limited to unbranched hydrocarbyl groups, e.g., C₈ hydrocarbylgroups include, but are not limited to, e.g., 2-ethylhexyl and2-propylpentyl groups. Exemplary unsubstituted, unbranched hydrocarbylgroups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, and octadecyl hydrocarbyl groups. R¹² in FormulaII is as described for R⁵ in Formula I.

In Formula II, the variable c is ≧1, e.g., ≧2, ≧5, ≧7, ≧8, ≧10, ≧12,≧14, ≧16, ≧18, ≧20, ≧22, ≧24, ≧26, ≧28, ≧30, ≧32, ≧34, ≧36, ≧38, ≧40,≧42, or ≧44. Additionally or alternatively, c may be ≦47, e.g., ≦44,≦42, ≦40, ≦38, ≦36, ≦34, ≦32, <30, ≦28, ≦26, ≦24, ≦22, ≦20, ≦18, ≦16,≦14, ≦12, ≦10, ≦8, ≦7, or ≦5. In Formula II, d is ≧0, e.g., ≧1, ≧5, ≧7,≧8, ≧10, ≧12, ≧14, ≧16, ≧18, ≧20, ≧22, ≧24, ≧26, ≧28, ≧30, ≧32, ≧34,≧36, ≧38, ≧40, ≧42, or ≧44. Additionally or alternatively, d may be ≦47,e.g., ≦44, ≦42, ≦40, ≦38, ≦36, ≦34, ≦32, ≦30, ≦28, ≦26, ≦24, ≦22, ≦20,≦18, ≦16, ≦14, ≦12, ≦10, ≦8, ≦7, or ≦5. Ranges of c and d values thatare expressly disclosed herein include ranges formed by any combinationof the above-recited individual values. In particular embodiments, cranges from about 5 to about 10, e.g., 8, and d ranges from about 5 toabout 10, e.g., 7, i.e., CH₃(CH₂)₇C═C(CH₂)₈—, also referred to as anoleyl group. The alkenyl group may optionally include two, three, fouretc., double bonded and/or triple bonded carbon atoms in the hydrocarbylchain. The double bond may have cis- or trans-configuration. Inparticular embodiments, the cis-configuration may be particularlyuseful. Where the hydrocarbyl chain of the carboxylic acid has more thanone carbon-carbon double bond, the bonds may have any combination ofcis- and/or trans-configurations. The double bonds may be arranged in aconjugated manner, e.g., conjugated (9Z, 11E)-linoleyl, or separated byat least one methylene group, e.g., linolenyl etc.) Other exemplarygroups include capryl, lauryl, myristyl, palmityl, isopalmityl, stearyl,isostearyl, oleyl, erucyl, palmitoleyl, etc.

In particular embodiments, the substituents of Formula II are selectedto provide an R⁶ group in Formula I comprising an oleyl orPEG-terminated oleyl group. In other embodiments, each R⁸ to R¹² is inselected to provide an oleyl or PEG-terminated oleyl group for R⁶ and/orR⁷ in Formula I. Exemplary compounds are depicted in Formulas III to V.

where R⁶ and R⁷ are as defined for Formula I or II.

In particular embodiments, of Formulas III to V, R⁶ and/or R⁷ is H,i.e., oleyl hydrogen phosphites. Compounds within the scope of FormulasIII to V include PEG-terminated analogues as well.

Exemplary phosphate esters within the scope of this description include,but are not limited to, n-dodecyl phosphate ester (lauryl phosphateester), di-n-dodecyl phosphate ester (di-lauryl phosphate ester),tri-n-dodecyl phosphate ester (tri-lauryl phosphate ester), n-tetradecylphosphate ester (myristyl phosphate ester), di-n-tetradecyl phosphateester (di-myristyl phosphate ester), tri-n-tetradecyl phosphate ester(tri-myristyl phosphate ester), n-hexadecyl phosphate ester (palmitylphosphate ester), di-n-hexadecyl phosphate ester (di-palmityl phosphateester), tri-n-hexadecyl phosphate ester (tri-palmityl phosphate ester),n-octadecyl phosphate ester (distearyl phosphate ester), di-n-octadecylphosphate ester (distearyl phosphate ester), tri-n-octadecyl phosphateester (tri-stearyl phosphate ester), n-9-octadecenyl phosphate ester(oleyl phosphate ester), di-9-octadecenyl phosphate ester (di-oleylphosphate ester), tri-9-octadecenyl phosphate ester (tri-oleyl phosphateester), n-eicosenyl phosphate ester, di-n-eicosenyl phosphate ester,tri-n-eicosenyl phosphate ester, n-dodecyl phosphate ester (laurylphosphate ester), n-hexadecyl phosphate ester (palmityl phosphateester), and n-octadecyl phosphate ester (stearyl phosphate ester).

Exemplary dihydrocarbyl hydrogen phosphites included, but are notlimited to, di-n-dodecyl hydrogen phosphite (dilauryl hydrogenphosphite), di-n-tetradecyl hydrogen phosphite (dimyristyl hydrogenphosphite), di-n-hexadecyl hydrogen phosphite (dipalmityl hydrogenphosphite), di-n-octadecyl hydrogen phosphite (distearyl hydrogenphosphite), di-n-octadecenyl hydrogen phosphite (dioleyl hydrogenphosphite), di-n-eicosenyl hydrogen phosphite, n-dodecyl hydrogenphosphite (lauryl hydrogen phosphite), n-hexadecyl hydrogen phosphite(palmityl hydrogen phosphite), n-octadecyl hydrogen phosphite (stearylhydrogen phosphite), 9-octadecenyl hydrogen phosphite (oleyl hydrogenphosphite), and n-eicosenyl hydrogen phosphite.

The friction-reducing composition may optionally include one or moresecondary friction-reducing components. Secondary friction-reducingcomponents may be selected from hydrocarbyl diols, particularly whereinthe hydrocarbyl group is selected from C₁₀ to C₂₅ alkyl groups, e.g.,octadecane-1-2-diol (described in concurrently filed PCT application:______, corresponding to U.S. Ser. No. 62/186,494 filed Jun. 30, 2015,entitled “Lubricant Compositions and Methods of Making and Using Same”,Attorney Docket No. 2015EM142); glycerol carbamates; e.g., oleylglycerol carbamate (described in concurrently filed PCT application______, corresponding to U.S. Ser. No. 62/186,503 filed Jun. 30, 2015,entitled “Glycerol Carbamate Based Lubricant Compositions and Methods ofMaking and Using Same”, Attorney Docket No. 2015EM141); hydrocarbylthioglycerols, e.g., octadecyl thioglycerol; and hydrocarbyl-substitutedglycerols, e.g., glycerol monostearate (described in concurrently filedPCT application ______, corresponding to U.S. Ser. No. 62/186,503 filedJun. 30, 2015, entitled “Lubricant Compositions Comprising DiolFunctional Groups and Methods of Making and Using Same”, Attorney DocketNo. 2015EM145) and certain amides and imidazolides, (described inconcurrently filed PCT application ______, corresponding to U.S. Ser.No. 62/186,509, filed Jun. 30, 2015, entitled “Lubricant Compositionsand Methods of Making and Using Same”, Attorney Docket No. 2015EM143),each of which is incorporated by reference in its entirety as a part ofthis disclosure.

Useful secondary friction-reducing components include, e.g., Vikinol™18, ColaLube™ 3410, ColaLube™ 3407, and additives under the tradenameColaMid™.

The secondary friction-reducing component may be present in the frictionreducing composition in an amount ≧ about 5.0 wt %, e.g., ≧ about 10.0wt %, ≧ about 15.0 wt %, ≧ about 20.0 wt %, ≧ about 25.0 wt %, ≧ about30.0 wt %, ≧ about 35.0 wt %, ≧ about 40.0 wt %, ≧ about 45.0 wt %, ≧about 50.0 wt %, ≧ about 55.0 wt %, ≧ about 60.0 wt %, ≧ about 65.0 wt%, ≧ about 70.0 wt %, ≧ about 75.0 wt %, ≧ about 80.0 wt %, ≧ about 85.0wt %, or ≧ about 90 wt %, based on the total weight of thefriction-reducing composition. Additionally or alternatively, thesecondary fiction-reducing component may be present in an amount ≦ about95 wt %, e.g., ≦ about 90.0 wt %, ≦ about 85.0 wt %, ≦ about 80.0 wt %,≦ about 75.0 wt %, ≦ about 70.0 wt %, ≦ about 65.0 wt %, ≦ about 60.0 wt%, ≦ about 55.0 wt %, ≦ about 50.0 wt %, ≦ about 45.0 wt %, ≦ about 40.0wt %, ≦ about 35.0 wt %, ≦ about 30.0 wt %, ≦ about 25.0 wt %, ≦ about20.0 wt %, ≦ about 15.0 wt %, or ≦ about 10.0 wt %, based on the totalweight of the friction-reducing composition. Ranges of the amount ofsecondary friction-reducing component that are expressly disclosedherein include ranges formed by any combination of the above-recitedindividual values, e.g., about 5.0 to about 95.0 wt %, about 10.0 toabout 90.0 wt %, about 15.0 to about 85.0 wt %, about 20.0 to about 80.0wt %, about 25.0 to about 75.0 wt %, about 30.0 to about 70.0 wt %,about 35.0 to about 65.0 wt %, about 40.0 to about 60.0 wt %, about 45.0to about 55.0 wt %, etc.

Methods of Making the Lubricant Composition

Lubricant compositions described herein can be made by mixing afriction-reducing composition described above and at least one base oilcomposition, comprising about 1.0 to about 15.0 wt % water. The methodmay additionally include mixing the base oil prior to blending with thefriction-reducing agent. In some embodiments, the mixture of the baseoil and the friction reducing agent is heated during mixing, e.g., for5-48 hours at a temperature of about 30 to about 70° C., e.g., about 24hours at about 60° C. In some methods, the heating includes providing anitrogen head pressure to the heating vessel of about 30 to about 50psi. Mixing at speeds of about 2000 to about 5000 rpm. Typically,mixtures are cooled for 10-24 hours at about 25° C. before testing oruse.

Methods of Drilling

Lubricant compositions described herein are useful in any number ofdrilling methods. One exemplary method comprises mixing afriction-reducing composition and at least one base oil, comprisingabout 1.0 to about 15.0 wt % water; and introducing the lubricantcomposition into the well.

The step of introducing can comprise pumping the lubricant compositioninto the well. The pumping may be done continuously, i.e., providing aconstant flow of lubricant composition, periodically or intermittently,i.e., alternating between periods of flow and no flow of lubricantcomposition. Particular methods further include continuously,periodically, or intermittently providing a second amount offriction-reducing composition to the lubricant composition alreadyprovided to the well. In some methods, the continuous provision of thefriction reducing composition provides an overall reduction in theamount of friction-reducing agent used during the drilling process.Alternatively, the continuous provision of the friction-reducing agentmay allow smoother drilling operation of the drilling process. The wellcan be, without limitation, an oil, gas, or water production well, or aninjection well. Methods may further include one or more steps ofadvancing a downhole tool in the well.

The introduced lubricant composition may be exposed to temperatures inthe well ranging from a low of about 70° C., 80° C., 90° C., 100° C., or125° C. to a high of about 170° C., and pressures ranging from ambientpressure to a high of about 100 bar (10,000 kPa), 200 bar (20,000 kPa),300 bar (30,000 kPa), 400 bar (40,000 kPa), 500 bar (50,000 kPa), or 600bar (60,000 kPa). The introduced lubricant composition may be utilizedwhen system components have rotation speed of ≦ about 1000 rpm, e.g., ≦about 800 rpm, ≦ about 700 rpm, and ≧ about 0 rpm, such as from 1 to1000 rpm. The introduced lubricant composition may also be utilized withminimal rotation but instead longitudinal motion at a speed of ≦10,000m/hr (meters per hour); ≦1,000 m/hr; ≦100; and/or ≦10m/hr.

According to an embodiment, the well penetrates a reservoir or islocated adjacent to a reservoir. The methods can further include thestep of removing at least a portion of the lubricant composition afterthe step of introducing. The methods can include any number ofadditional optional steps. For example, some methods include one or moreof the following optional steps: mounting and cementing of well pipes inthe first well; mounting of a blowout preventer or lubricator in the topof the well; drilling, at a distance from the well, a second wellagainst a section of the first well to the effect that the second wellgets into operational contact with the first well; mounting andcementing of well pipes in the second well; mounting of a blowoutpreventer or lubricator in the top of the second well; whereafter thedrilling from one of the first or second well continues down into thereservoir and the other well which is not drilled to the reservoir isfilled wholly or partially with a fluid and a drilling tool is placed inthe other well and the other well is subsequently closed so that theother well can be accessed at a later point in time, and that the toolis left in the other well so that this tool can establish a connectionto the one of the first or second wells into which the drillingcontinued.

Still other optional steps include one or more of the following:calculating a desired path for a well of interest relative to areference well; measuring a position of the well of interest relative tothe reference well at a location along a wellbore of the well;calculating an actual path of the well of interest based at least inpart on the measured position of the well of interest relative to the atleast one reference well; comparing the actual path of the at least onewell of interest to the desired path of the well of interest; andadjusting a drilling system to modify the actual path of the well ofinterest based at least in part on a deviation between the actual pathof the well of interest and the desired path of the well of interest.

Experimental

Viscosity Index is determined from the Kinematic viscosity according toASTM D2270-10e1.

Kinematic Viscosity is determined according to ASTM D445.

Coefficient of Friction (CoF) is determined using a block-on-ringtribometer available from CETR, Inc., USA. The block is made of P110steel and the ring is a nitrided Timken ring having a radius of 17.5 mm(35 m OD) and a width of 6.35 mm. The blocks are machined to a finalsurface roughness, R_(a), of 0.18 μm. The ring has a surface roughness,R_(a), of about 0.01 μm. The ring is partially submerged into 100 ml ofthe fluid to be tested such that about 10 ml of the ring is beneath thesurface of the fluid. The block applies a 5.6 kg load on the ring.Testing is performed at 25° C. The ring is turned at 25 rpm, 50 rpm, 100rpm, 250 rpm, 500 rpm, and 750 rpm for 4 mins at each speed to obtainthe Stribeck response of the fluid. It should be noted that initialmeasurements may be significantly affected by changes in the contactingsurfaces, reaction of surface active components, entrainment of fluid inthe inlet zone of the instrument etc. Care should be taken to allowsteady state operation to be achieved before the coefficient of frictionis recorded. Typically, steady state boundary friction response isobtained by continuing the test for an additional 30 mins at 25 rpm. Thesteady state boundary friction response is reported as the coefficientof friction is the results reported herein.

Operating Torque: Drilling operations may be constrained due to torquelimits at the drilling rig. The constraints may be due to maximum torquethat a driver can deliver and/or the maximum torque that the drillingstring can withstand before metal failure will occur; such constraintsare therefore different for different drilling rigs due to either thesize of the driver and/or the drill string in use. The Operating Torquecan be measured by a dedicated device (e.g., a torque sub) and/or bymeasured power usage by the driver. Typically drilling operations areconducted with at least a 10% safety margin between the Operating Torqueand the torque limit. When the Operating Torque is nearing or exceedingwhat is considered to be a reasonable value, this will limit the lengthof the wellbore that is achievable. Operating changes can be performedto reduce the Operating Torque, e.g., reducing the rate of penetration(the forward rate of drilling), removing accumulated cuttings from thewellbore, removing the drill string from the wellbore andreplacing/refurbishing worn components, and/or reducing the amount oflow gravity solids (ground down cuttings) from the circulating base oilcomposition. These steps to reduce the operating torque can be expensiveand time consuming, and may offer little benefit. Therefore use of afriction reduction additive is beneficial to reduce the operating torqueso as to increase rate of penetration and/or allow for greater length ofthe wellbore.

EXAMPLE 1

In Example 1, a base oil comprising about 210 g Escaid™ 110, about 8.0 gVG Plus™, and about 7 g of lime are added and mixed for about 5 min.About 9.0 g of MegaMul™ is added to the resulting mixture followed byabout 5 min. of further mixing. About 18.5 g calcium chloride is mixedwith about 50 ml of water and added to the mixture, followed by about225 g of barite weighting agent. The combination is mixed for about 10min. before addition of about 6.0 grams of Versitrol M™ followed by anadditional 5 min. of mixing. Thereafter, about 45.0 g of Rev Dust™ isadded followed by 10 min. of mixing. The base oil is hot aged for about16 hrs. at a temperature of about 120° C. The coefficient of friction(CoF) of the base oil is measured as a baseline and reported in Table I.

EXAMPLE 2

In Example 2, Example 1 is substantially repeated, except that thecomposition comprises about 97 wt % of composition of Example 1 andabout 3 wt % of a conventional friction reducing agent available underthe tradename Ultralube II, available from Integrity Industries, Inc.,Kingsville, Tex., USA. The mixture is covered and heated to about 60° C.while being mixed for about 60 min. The sample is cooled at about 25° C.for 16 hrs. The cooled sample is mixed for about 30 min. at about 4000rpm. The coefficient of friction (CoF) of the sample is measured andreported in Table I.

EXAMPLE 3

In Example 3, Example 2 is substantially repeated, except that thecomposition comprises about 97 wt % of composition of Example 1 andabout 3 wt % dioleyl hydrogen phosphite. The coefficient of friction(CoF) of the base oil and additive package is measured and reported inTable I.

EXAMPLE 4

In Example 4, Example 2 is substantially repeated, except that thecomposition comprises about 97 wt % of composition of Example 1 andabout 3 wt % aliphatic phosphate ester, commercially available fromColonial Chemical, Inc. as ColaLube™ 3410. The coefficient of friction(CoF) of the base oil and additive package is measured and reported inTable I.

EXAMPLE 5

In Example 5, Example 2 is substantially repeated, except that thecomposition comprises about 97 wt % of composition of Example 1 andabout 3 wt % of a PEG monooleyl ether phosphate ester, commerciallyavailable from Colonial Chemical, Inc. as ColaLube™. The coefficient offriction (CoF) of the base oil and additive package is measured andreported in Table I.

TABLE I Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 CoF 0.17 0.14 0.12 0.085 0.125Relative CoF* 1 0.82 0.70 0.5 0.735 % Reduction CoF** — 18 29 50 26*Relative CoF is as compared to Example 1. **% Reduction CoF = 1 −Relative CoF.

Particular Embodiments

This invention relates to:

Embodiment 1. A lubricant composition suitable for use in drillingoperations, comprising:

-   -   a) about 90 to 99 wt % of at least one base oil composition, the        base oil composition comprising about 1.0 to about 15.0 wt %        water, and    -   b) from about 1.0 to about 10.0 wt % of a friction-reducing        composition comprising: at least one compound represented by        Formula I:

wherein R¹, R², R³ and R⁴ is selected from the group consisting of H andbranched or unbranched, substituted or unsubstituted C₁ to C₂₀hydrocarbyl groups;

R⁵ is selected from the group consisting of H and branched orunbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbyl groups orpolyethylene glycol groups represented by the formula O(CH₂CH₂O)_(n)R′,wherein R′ is H or a branched or unbranched, substituted orunsubstituted C₁ to C₂₀ hydrocarbyl groups and n is from 1 to about 50;

each R⁶ and R⁷ is individually selected from the group consisting of H,branched or unbranched, substituted or unsubstituted C₁ to C₁₀₀hydrocarbyl groups, branched or unbranched, substituted or unsubstitutedC₁ to C₁₀₀ alkoxyhydrocarbyl groups;

wherein y is an integer from 1 to 47; and

wherein z is an integer from 0 to 47.

Embodiment 2. A method of making a lubricant composition suitable foruse in drilling operations, comprising:

a) providing at least one base oil composition, the base oil compositioncomprising about 1.0 to about 15.0 wt % water, and

b) combining about 90 to about 99.0 wt % of the base oil compositionwith about 1.0 to about 10.0 wt % of the composition of Embodiment 1.

Embodiment 3. A lubricant composition suitable for use in drillingoperations made by a process, comprising:

a) providing at least one base oil composition, the base oil compositioncomprising about 1.0 to about 15.0 wt % water, and

b) combining about 90 to about 99.0 wt % of the base oil compositionwith about 1.0 to about 10.0 wt % of the composition of Embodiment 1.

Embodiment 4. A method of drilling a wellbore comprising:

a) providing a friction-reducing composition prepared by mixing i)greater than or equal to about 90 wt % of at least one base oilcomposition, the base oil composition comprising about 1.0 to about 15.0wt % water, and ii) from about 1.0 to about 10.0 wt % of the compositionof Embodiment 1; and

b) introducing the lubricant composition into the wellbore.

Embodiment 5. Any of Embodiments 1 to 4, wherein y is about 5 to about10 and z is about 5 to about 10.

Embodiment 6. Any of Embodiments 1 to 5, wherein R¹, R², R³ and R⁴ is Hand R⁵ is methyl.

Embodiment 7. Any of Embodiments 1 to 4, wherein y, z, and R¹ to R⁵ areselected to give an oleyl group, an erucyl group, or a palmitoleylgroup.

Embodiment 8. Any of Embodiments 1 to 4, wherein y is about 5 to about10, z is about 5 to about 10, n is 2 to 10, each R¹ to R⁴ is H and R′ ismethyl.

Embodiment 9. Any of Embodiments 1 to 4, wherein at least one or R⁶ andR⁷ is selected from hydrocarbyl groups represented by Formula II:

R¹²(CR¹¹ ₂)_(z)CR¹⁰═CR⁹(CR⁸ ₂)_(y)O—  Formula II

wherein each R⁸, R⁹, R¹⁰ and R¹¹ is selected from the group consistingof H and branched or unbranched, substituted or unsubstituted C₁ to C₂₀hydrocarbyl groups;

R¹² is selected from the group consisting of H and branched orunbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbyl groups orpolyethylene glycol groups having the formula O(CH₂CH₂O)_(n)R″, whereinR″ is H or a branched or unbranched, substituted or unsubstituted C₁ toC₂₀ hydrocarbyl group and n is from 1 to about 50;

y of Formula II is an integer from 1 to 47; and

z of Formula II is an integer from 0 to 47.

Embodiment 10. Embodiment 9, wherein y of Formula II is about 5 to about10 and z of Formula II is about 5 to about 10.

Embodiment 11. Embodiment 9, wherein R⁸, R⁹, R¹⁰ and R¹¹ are H and R¹²is methyl.

Embodiment 12. Embodiment 9, wherein y of Formula II, z of Formula II,and R⁸ to R¹² are selected to give an oleyl group, an erucyl group, or apalmitoleyl group.

Embodiment 13. Any of Embodiments 1 to 4, wherein y of Formula II isabout 5 to about 10, z of Formula II is about 5 to about 10, n is 2 to10, R⁸, R⁹, R¹⁰ and R¹¹ is H and R″ is H.

Embodiment 14. Any of Embodiments 1 to 4 wherein the compoundrepresented by Formula I is selected from the group consisting ofn-dodecyl phosphate ester (lauryl phosphate ester), di-n-dodecylphosphate ester (di-lauryl phosphate ester), tri-n-dodecyl phosphateester (tri-lauryl phosphate ester), n-tetradecyl phosphate ester(myristyl phosphate ester), di-n-tetradecyl phosphate ester (di-myristylphosphate ester), tri-n-tetradecyl phosphate ester (tri-myristylphosphate ester), n-hexadecyl phosphate ester (palmityl phosphateester), di-n-hexadecyl phosphate ester (di-palmityl phosphate ester),tri-n-hexadecyl phosphate ester (tri-palmityl phosphate ester),n-octadecyl phosphate ester (distearyl phosphate ester), di-n-octadecylphosphate ester (distearyl phosphate ester), tri-n-octadecyl phosphateester (tri-stearyl phosphate ester), n-9-octadecenyl phosphate ester(oleyl phosphate ester), di-9-octadecenyl phosphate ester (di-oleylphosphate ester), tri-9-octadecenyl phosphate ester (tri-oleyl phosphateester), n-eicosenyl phosphate ester, di-n-eicosenyl phosphate ester,tri-n-eicosenyl phosphate ester, n-dodecyl phosphate ester (laurylphosphate ester), n-hexadecyl phosphate ester (palmityl phosphateester), and n-octadecyl phosphate ester (stearyl phosphate ester).

Embodiment 15. Any of Embodiments 1 to 4, wherein the compoundrepresented by Formula I is selected from the group consisting ofdihydrocarbyl hydrogen phosphites including, but not limited to,di-n-dodecyl hydrogen phosphite (dilauryl hydrogen phosphite),di-n-tetradecyl hydrogen phosphite (dimyristyl hydrogen phosphite),di-n-hexadecyl hydrogen phosphite (dipalmityl hydrogen phosphite),di-n-octadecyl hydrogen phosphite (distearyl hydrogen phosphite),di-n-octadecenyl hydrogen phosphite (dioleyl hydrogen phosphite),di-n-eicosenyl hydrogen phosphite, n- dodecyl hydrogen phosphite (laurylhydrogen phosphite), n-hexadecyl hydrogen phosphite (palmityl hydrogenphosphite), n-octadecyl hydrogen phosphite (stearyl hydrogen phosphite),9-octadecenyl hydrogen phosphite (oleyl hydrogen phosphite), andn-eicosenyl hydrogen phosphite.

Embodiment 16. A method of providing a lubricant composition to adrilling operation, comprising:

a) providing to said drilling operation at least one base oilcomposition, the base oil composition comprising about 1.0 to about 15.0wt % water,

b) operating said drilling operation for a period of time with said baseoil composition, and

c) adding to the drilling operation a friction-reducing compositionaccording to any Embodiment described herein.

Embodiment 17. Embodiment 16 wherein adding the friction-reducingcomposition comprises adding the friction-reducing composition at a ratesufficient to provide a concentration of the friction reducing additivein the lubricant composition of about 0.5% to about 10.0 wt % after atime period of about 3 hours to 180 days.

Embodiment 18. Any of Embodiments 16 to 17, wherein said drillingoperation comprises one or more of: introducing a drill string;introducing coiled tubing; introducing casing; introducing screens;introducing tools for cleaning, fracturing, and perforating; rotatingdrill string; advancing the wellbore; withdrawing a drill string; and/orwithdrawing coiled tubing.

Embodiment 19. Any of Embodiments 16 to 18, wherein adding the frictionreducing composition comprises adding the friction-reducing compositionintermittently to maintain a desired Operating Torque.

Embodiment 20. Any of Embodiments 16 to 19, wherein said drillingoperation has an Operating Torque <95%, e.g., ≦ about 90.0%, ≦ about85.0%, ≦ about 80.0%, ≦ about 75.0%, ≦ about 70.0%, of the OperatingTorque of the same drilling operation performed with the base oilcomposition, but lacking the friction-reducing composition.

Embodiment 21. A method of preparing a well bore comprising providing alubricant composition according to any Embodiment described herein.

Embodiment 22. A method of producing hydrocarbons comprising providing alubricant composition according to any Embodiment described herein.

As demonstrated above, embodiments of the invention provide newlubricating compositions that may be useful in a variety of lubricatingoperations, e.g., well-bore extension, well completion, etc. The newlubricants may have one or more of the following advantages. Forexample, the compositions may have a lower coefficient of friction thatcurrently known compositions, thereby facilitating well-bore lengths notbefore achievable. In some instances, the compositions may have betterdurability or persistence in the drilling environment. Othercharacteristics and additional advantages are apparent to those skilledin the art.

It is believed that some diols surprisingly interact with iron and/oriron-containing particles in the drilling environment. It had beenthought that the reduction in coefficient of friction is to the amountof iron that the friction-reducing composition can adsorb (i.e., theμmols of iron that could be adsorbed by a gram of friction-reducingcomposition). Surprisingly, it has been found that greater reduction inthe coefficient of friction may be achieved by selecting thefriction-reducing composition based, not on the adsorption capacity, butrather upon the free energy of adsorption, ΔG°_(abs). When properlyselected so that the friction reducing composition has a free-energy ofadsorption for iron ≦ about −18.0 kJ/mol, e.g., ≦ about −20.0 kJ/mol, ≦about −22.0 kJ/mol, ≦ about −24.0 kJ/mol, ≦ about −26.0 kJ/mol, ≦ about−28.0 kJ/mol, ≦ about −30.0 kJ/mol, ≦ about −35.0 kJ/mol show improvedreduction in the coefficient of friction. Particular compositions have afree energy of adsorption of about −18.0 to about −35.0 kJ/mol, about−20.0 to about −30.0 kJ/mol, about −22.0 to about −28.0 kJ/mol, about−24.0 to about −26.0 kJ/mol. In this way, less friction-reducingcomposition may need to be used than otherwise believed.

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents and/or testing procedures to the extent they arenot inconsistent with this text. As is apparent from the foregoinggeneral description and the specific embodiments, while forms of theinvention have been illustrated and described, various modifications canbe made without departing from the spirit and scope of the invention.Accordingly, it is not intended that the invention be limited thereby.For example, the compositions described herein may be free of anycomponent, or composition not expressly recited or disclosed herein. Anymethod may lack any step not recited or disclosed herein. Likewise, theterm “comprising” is considered synonymous with the term “including.”And whenever a method, composition, element or group of elements ispreceded with the transitional phrase “comprising,” it is understoodthat we also contemplate the same composition or group of elements withtransitional phrases “consisting essentially of,” “consisting of,”“selected from the group of consisting of,” or “is” preceding therecitation of the composition, element, or elements and vice versa.

What is claimed is:
 1. A lubricant composition suitable for use indrilling operations, comprising: a) about 90 to 99 wt % of at least onebase oil composition, the base oil composition comprising about 1.0 toabout 15.0 wt % water, and b) from about 1.0 to about 10.0 wt % of afriction-reducing composition comprising: at least one compoundrepresented by Formula I:

wherein each R¹, R², R³, and R⁴ is selected from the group consisting ofH and branched or unbranched, substituted or unsubstituted C₁ to C₂₀hydrocarbyl groups; R⁵ is selected from the group consisting of H andbranched or unbranched, substituted or unsubstituted C₁ to C₂₀hydrocarbyl groups and polyethylene glycol groups having the formulaO(CH₂CH₂O)_(n)R′, wherein R′ is H or a branched or unbranched,substituted or unsubstituted, C₁ to C₂₀ hydrocarbyl groups and n is from1 to about 50; each R⁶ and R⁷ is individually selected from the groupconsisting of H, branched or unbranched, substituted or unsubstituted C₁to C₁₀₀ hydrocarbyl group and branched or unbranched, substituted orunsubstituted C₁ to C₁₀₀ alkoxyhydrocarbyl group; y is an integer from 1to 47; and z is an integer from 0 to
 47. 2. The lubricant composition ofclaim 1, wherein y is about 5 to about 10 and z is about 5 to about 10.3. The lubricant composition of claim 1, wherein each R1, R2, R3, and R4is H and R5 is methyl.
 4. The lubricant composition of claim 1, whereiny, z, and R1 to R5 are selected to give an oleyl group, an erucyl group,or a palmitoleyl group.
 5. The lubricant composition of claim 1, whereiny is about 5 to about 10, z is about 5 to about 10, n is 2 to 10, eachR1, R2, R3, and R4 is H and R′ is methyl.
 6. The lubricant compositionof claim 1, wherein at least one of R6 and R7 is selected fromhydrocarbyl groups represented by Formula II:R¹²(CR¹¹ ₂)_(z)CR¹⁰═CR⁹(CR⁸ ₂)_(y)O—  Formula II wherein each R⁸, R⁹,R¹⁰, and R¹¹ is selected from the group consisting of H and branched orunbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbyl groups;wherein R¹² is selected from the group consisting of H and branched orunbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbyl groupsand polyethylene glycol groups represented by the formulaO(CH₂CH₂O)_(n)R″, wherein R¹¹ is H or a branched or unbranched,substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group and n is from 1to about 50; y of Formula II is an integer from 1 to 47; and z ofFormula II is an integer from 0 to
 47. 7. The lubricant composition ofclaim 6, wherein each R8, R9, R10, and R11 is H and R12 is methyl. 8.The lubricant composition of claim 1, wherein y of Formula II is about 5to about 10, z of Formula II is about 5 to about 10, n is 2 to 10, eachR8, R9, R10, and R11 is H and R″ is H.
 9. A method of making a lubricantcomposition suitable for use in drilling operations, comprising: a)providing at least one base oil composition, the base oil compositioncomprising about 1.0 to about 15.0 wt % water, and b) combining about 90to about 99.0 wt % of the base oil composition with about 1.0 to about10.0 wt % of a friction-reducing composition comprising: a compoundrepresented by Formula I:

wherein each R¹, R², R³, and R⁴ is selected from the group consisting ofH and branched or unbranched, substituted or unsubstituted C₁ to C₂₀hydrocarbyl groups; R⁵ is selected from the group consisting of H andbranched or unbranched, substituted or unsubstituted C₁ to C₂₀hydrocarbyl groups and polyethylene glycol groups represented by theformula O(CH₂CH₂O)_(n)R′, wherein R′ may be H or a branched orunbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group andn is from 1 to about 50; R⁶ and R⁷ is individually selected from thegroup consisting of H, branched or unbranched, substituted orunsubstituted C₁ to C₁₀₀ hydrocarbyl groups and branched or unbranched,substituted or unsubstituted C₁ to C₁₀₀ alkoxyhydrocarbyl groups; y isan integer from 1 to 47; and z is an integer from 0 to
 47. 10. Themethod of claim 9, wherein each R¹, R², R³, and R⁴ is H and R⁵ ismethyl.
 11. The method of claim 9, wherein y is about 5 to about 10, zis about 5 to about 10, n is 2 to 10, each R1, R2, R3, and R4 is H andR′ is methyl.
 12. The method of claim 9, wherein at least one of R6 andR7 is selected from hydrocarbyl groups represented by Formula II:R¹²(CR¹¹ ₂)_(z)CR¹⁰═CR⁹(CR⁸ ₂)_(y)O—  Formula II wherein each R⁸, R⁹,R¹⁰, and R¹¹ is selected from the group consisting of H and branched orunbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbyl groups;R¹² is selected from the group consisting of H and branched orunbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbyl groupsand polyethylene glycol groups represented by the formulaO(CH₂CH₂O)_(n)R″, wherein R″ is H or a branched or unbranched,substituted or unsubstituted C₁ to C₂₀ hydrocarbyl groups and n may befrom 1 to about 50; y of Formula II is an integer from 1 to 47; and z ofFormula II is an integer from 0 to
 47. 13. The method of claim 9,wherein each R⁸, R⁹, R¹⁰, and R¹¹ is H and R¹² is methyl.
 14. The methodof claim 9, wherein y of Formula II is about 5 to about 10, z of FormulaII is about 5 to about 10, n is 2 to 10, each R8, R9, R10, and R11 is Hand R″ is H.
 15. A method of drilling a wellbore comprising: a)providing a friction-reducing composition prepared by mixing i) greaterthan or equal to about 90 wt % of at least one base oil composition, thebase oil composition comprising about 1.0 to about 15.0 wt % water, andii) from about 1.0 to about 10.0 wt % of a friction-reducing compositioncomprising: a compound represented by Formula I:

wherein each R¹, R², R³, and R⁴ is selected from the group consisting ofH and branched or unbranched, substituted or unsubstituted C₁ to C₂₀hydrocarbyl groups; R⁵ is selected from the group consisting of H andbranched or unbranched, substituted or unsubstituted C₁ to C₂₀hydrocarbyl groups and polyethylene glycol groups represented by theformula O(CH₂CH₂O)_(n)R′, wherein R′ may be H or a branched orunbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbyl group andn is from 1 to about 50; each R⁶ and R⁷ is individually selected fromthe group consisting of H, branched or unbranched, substituted orunsubstituted C₁ to C₁₀₀ hydrocarbyl groups, and branched or unbranched,substituted or unsubstituted C₁ to C₁₀₀ alkoxyhydrocarbyl groups; y isan integer from 1 to 47; z is an integer from 0 to 47; and b)introducing the lubricant composition into the wellbore.
 16. The methodof claim 15, wherein y, z, and R1 to R5 are selected to give an oleylgroup, an erucyl group, or a palmitoleyl group.
 17. The method of claim15, wherein at least one of R6 and R7 is selected from hydrocarbylgroups represented by Formula II:R¹²(CR¹¹ ₂)_(z)CR¹⁰═CR⁹(CR⁸ ₂)_(y)O—  Formula II wherein each R⁸, R⁹,R¹⁰, and R¹¹ is selected from the group consisting of H and branched orunbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbyl groups;R¹² is selected from the group consisting of H and branched orunbranched, substituted or unsubstituted C₁ to C₂₀ hydrocarbyl groupsand polyethylene glycol groups having the formula O(CH₂CH₂O)_(n)R″,wherein R″ is H or a branched or unbranched, substituted orunsubstituted C₁ to C₂₀ hydrocarbyl group and n is from 1 to about 50; yof Formula II is an integer from 1 to 47; and z of Formula II is aninteger from 0 to
 47. 18. The method of claim 15, wherein y of FormulaII is about 5 to about 10, z of Formula II is about 5 to about 10, n is2 to 10, each R⁸, R⁹, R¹⁰, and R¹¹ is H and R″ is H.
 19. A method ofproviding a lubricant composition to a drilling operation, comprising:a) providing to said drilling operation at least one base oilcomposition, the base oil composition comprising about 1.0 to about 15.0wt % water, b) operating said drilling operation for a period of timewith said base oil composition, and c) adding to the drilling operationa friction-reducing composition according to claim
 1. 20. The method ofclaim 19, wherein adding the friction-reducing composition comprisesadding the friction-reducing composition at a rate sufficient to providea concentration of the friction reducing additive in the lubricantcomposition of about 0.5% to about 10.0 wt % after a time period ofabout 3 hours to 180 days.
 21. The method of claim 19, wherein saiddrilling operation comprises one or more of: introducing a drill string;introducing coiled tubing; introducing casing; introducing screens;introducing tools for cleaning, fracturing, and perforating; rotatingdrill string; advancing the wellbore; withdrawing a drill string; and/orwithdrawing coiled tubing.
 22. The method of claim 19, wherein addingthe friction reducing composition comprises adding the friction-reducingcomposition intermittently to maintain a desired Operating Torque. 23.The method of claim 19, wherein said drilling operation has an OperatingTorque <95% of the Operating Torque of the same drilling operationperformed with the base oil composition, but lacking thefriction-reducing composition.
 24. A method of producing hydrocarbonscomprising providing a lubricant composition according to claim 1 to adrilling operation.
 25. The lubricant composition of claim 1, whereinthe base oil comprises base oil, wherein the base oil is present in thelubricant composition in the range from about 50.0 to about 99.0 wt %and the friction-reducing composition is present in the lubricantcomposition in the amount of about 0.1 to about 6.0 wt %.